Polyfunctional polyolefins

ABSTRACT

A grafted polyolefin polymers having high polarity produced by grafting bi-functional N-substituted diacids to maleated or other functional group grafted polyolefin. The new polymers exhibit improved water miscibility, compatability and good adhesion to polar materials such as nylon, polyester, glass, and metal substrates.

FIELD OF THE INVENTION

This invention relates to polyfunctional polyolefins and morespecifically to polyfunctional polybutene polymers. The invention isalso directed to methods of introducing the proper level offunctionality in polybutylene materials. The invention is furtherdirected to polycarboxylic functionalized polyolefins and methods ofmaking which include preforming of an adduct that contains at leastthree or more functional carboxylic acid groups which can then begrafted via a free radical initiated reaction to active sites inpolyolefins such as polybutylene and polypropylene polymers.

The instant invention also provides a method for improving the polarityof polybutylene by grafting a small molecule, which contains severalacid functional groups to the hydrocarbon backbone of polybutylene. Theincreased functionality offers an abundant potential for various choicesof chemistry in polymer modification.

The present invention also relates to a process for producing a graftmodified polyolefin having good adhesion to polar materials such asnylon, polyester, glass, metal, etc.

The invention further relates to a superior functionalized polybutylenewhich is suitable for several new applications such as for hot meltadhesives and for emulsions. Applicants have discovered a new methodwhich results in the grafting of small molecules of bi-functionalN-substituted diacids to an unsaturated carboxylic acid, such as maleicanhydride, which can be grafted to polybutylene. The small chelate,iminodiacetic acid (IDA), is very effective because it is very reactiveand can coordinate with most metals to form stable structures. Theincreased functionality of the grafted polymer provides higher adhesivestrength in adhesive joints in a number of different substrates.

BACKGROUND OF THE INVENTION

Because of the unique set of properties of polyolefins such aspolybutylene and polypropylene, particularly their high compliancecompared to other polyolefins and their comparatively low meltingtemperature, a functionalized version becomes an excellent candidate tofill the requirements of a structural hot melt adhesive. Polybutylenewithout functional groups lacks the functionality or polarity needed forthe adhesion to high surface energy substrates, a necessarycharacteristic for both hot melt adhesives and their constituents.

Polybutylene, like other polyolefins, has no functionality on the chainand therefore artifacts made from this polymer have very low surfacefree energy and can not be decorated by painting or printing. In thepast, researchers have reacted functional groups on the surface ofpolyolefins by various means using highly oxidative techniques to inducebonding sites with reagents leaving hydroxyl or carboxyl groups. Also,melt reactions have been carried out to functionalize the bulk of thepolyolefin material by a free radical initiated reaction induced byorganic peroxides.

A large number of polymer companies commercially offer functionalizedpolyolefin materials such as acrylated and maleated polypropylene andpolyethylene. Techniques used to modify these polymers provide one or,at most, two acid groups per grafting site. The present inventor hasfound that by increasing the number of functional groups to three orgreater per grafting site one can substantially improve the polarity andhence improve the polymer's performance in several end use application.

Additionally, there is an ever increasing impetus to replace orsupplement solvent-based polymer coating compositions with aqueous-basedcounterparts due to the environmental toxicity and flammability problemsposed by the use of volatile organic solvents. However, even whereaqueous-based polymer compositions have been devised, their productionhas usually entailed the intermediate use of organic solvents, requiringsubsequent removal which is costly and time-consuming, or theincorporation of a certain amount of a solvent in the final compositionwhich acts to ensure proper film-formation on coating (known as acoalescing solvent). There is therefore also now increasing pressure tosignificantly reduce or eliminate the volatile organic contents (VOCS)in aqueous-based polymer composition syntheses both as components intheir production (even if subsequently removed) and in the resultingcomposition as an aid to film coalescence.

In the present invention, applicants have found unexpectedly thatmulti-carboxylic acid as the functional group can co-ordinate veryeffectively with most metals to form stable, e.g. octahedral, anioniccomplexes. For example, two moles of iminodiacetic acid contain fourcarboxylic acid groups, which can react with metal ions to form to havestability constant in excess of 10¹⁰. The introduction of carboxylicfunctionality into polyolefins allow for more water solubility as wellas production of water borne products which are environmentallydesirable.

SUMMARY OF THE INVENTION

The present invention is directed to a grafted polyolefin comprising thereaction product of: (a) a polyolefin which had been grafted with anunsaturated carboxylic acid anhydride or acid thereof; and (b) an aminocarboxylic acid.

The instant invention is also directed to a grafted polyolefincomprising the reaction product of: (a) a polyolefin; and (b) an aminocarboxylic acid.

The invention further relates to a grafted polyolefin comprising thereaction product of: (a) a polyolefin; (b) an unsaturated carboxylicacid anhydride or unsaturated carboxylic acid; and (c) an aminocarboxylic acid.

The invention also describes a grafted polybutylene polymer comprisingthe free radical grafting reaction product of polybutylene andiminodiacetic acid.

In a further aspect of the invention, there is described a graftedpolybutylene polymer comprising the free radical grafting reactionproduct of polybutylene and maleic anhydride further reacted withiminodiacetic acid.

The invention also provides ( 1) a compound (adduct), made by reactingmaleic acid anhydride ( ester ) with iminodiacetic acid or a saltthereof and useful for grafting polyolefins, which compound has aformula selected from the group consisting of formula [1], [2], [3]below and mixtures thereof; (2) a process for making multi-functionalpolyolefins by grafting polyolefin such as polypropylene or polybutylenewith such compound; and (3) a multifunctionalized polyolefin made bysuch process. The compound (adduct) formula selected from the groupconsisting of formula [1], [2], [3] below and mixtures thereof:

wherein M⁺is Na⁺, K⁺, Li⁺, or Cs⁺

The compound (monomer) can also further react to form dimer, trimer andoligomer.

The invention further provides a grafted polybutylene homopolymer orcopolymer having 1-50, preferably 1-30, more preferably 2-15 molepercent of an alpha olefin having from 2-8 carbon atoms, wherein thepolybutylene is grafted with from about 0.01 to about 30, preferablyfrom about 1 to about 15, more preferably from about 3 to about 10weight percent of iminodiacetic acid

The present invention also provides an adhesive composition comprisingthe multi-functional polyolefins, particularly multi-functionalpoly-1-butene, described above. Particularly, the present invention alsoprovides an adhesive composition comprising the reaction product of (a)a polybutylene compound consisting of polybutylene modified by graftingthereto an unsaturated monomer bearing an acid, ester or acid anhydridegroup, with (b) an amino polycarboxylic acid compound or a salt thereofbearing at least one primary or secondary amine groups, which arereactive with the anhydride group.

The invention is also directed to an emulsion composition comprising:(1) 25 to 55 weight percent of a grafted polyolefin comprising thereaction product of (i) a polyolefin, (ii) an ethylenically unsaturatedmonomer having functionality capable of reacting with an amino group and(iii) an amino carboxylic acid or a salt thereof; (2) a minor amount upto 10 weight percent of a surfactant; and (3) 55 to 80 weight percentwater.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

While the present invention is described in connection with preferredembodiments, it will be understood that it is not intended to limit theinvention to those embodiments. On the contrary, it is intended to coverall alternatives, modifications, and equivalents as may be includedwithin the spirit and scope of the invention as defined by the appendedclaims.

The preferred mode of grafting the polyolefins is via free-radicalgrafting using peroxide initiators although other initiators such as azocompounds can be used. The organic peroxides which may be suitably usedin the present invention are those having a decomposition temperature ofpreferably from 80° C. to 230° C., preferably from 110° C. to 220° C.and more preferably from 110C. to 210° C.

Particularly preferred organic peroxide compounds have half lives at210° C. of from 1 to 30 seconds. Among these compounds, dicumylperoxide, monocumyl tert-butyl peroxide, di-tert-butyl peroxide,2,5-dimethyl-2,5-di-(tert-butylperoxy)-hexane and2,5-dimethyl-2,5-di-(tert-butylperoxy)-hex-3-yne are particularlynoteworthy. Other peroxides which can be used in the practice of thepresent invention include benzoylperoxide, acetylperoxide,di-t-butylperoxide, t-butylperoxylaurate, dicumylperoxide,1,3-bis(t-butylperoxyisoprypyl)benzene,1-4-bis(t-butylperoxypropyl)benzene, 2,5-di-(t-butylperoxy)hexane,t-butylperoxybenzoate, -butyl4,4-bis-(t-butylperoxy)-valerate,octanoylperoxide, p-methane hydroperoxide, and t-butylperoxyacetate;azobis-compounds such as azobisisobutylnitrile,2,2-azobis(2,4,4-trismethyvaleronitrile), and2,2-azobis(2-cyclopropylpropionitrile); inorganic peroxides such aspotassium persulfate, sodium persulfate, and ammonium persulfate may berecited.

The free radical-generator is generally used in the process according tothe invention in a sufficient quantity to make it possible to effect thegrafting. Furthermore, it is desirable that the quantity should notexceed the minimum quantity needed because any excess ofradical-generator results in a degradation of the polyolefin. Thequantity is usually at least 0.005 parts by weight per 100 parts byweight of polyolefin; it is in particular at least 0.01 part by weight,values of at least 0.02 parts by weight being the most advantageousones. In general the quantity does not exceed 1 part by weight per 100parts by weight of polyolefin, preferably 0.5 parts by weight, values ofnot more than 0.1 being the most recommended ones, for exampleapproximately 0.04 parts by weight.

The peroxide under proper temperature homolytically decomposes,generates a free radical which abstracts hydrogen from the tertiarycarbon of the polyolefin polymer, thus providing a reaction site forvinyl monomers or other labile molecules. The reaction is characterizedas a random free radical event reaction without any bias towarddistribution along the polymer chain.

The polyolefin homopolymers or copolymers are modified by grafting witha radically polymerizable unsaturated grafting compound selected fromthe group consisting of vinyl-polymerizable, unsaturated, hydrolyzablesilane compounds, carboxylic acids and derivatives, carboxylic acidanhydrides and derivatives, and mixtures thereof, in the presence of afree radical generator. In the present invention, the ethylenicallyunsaturated grafting monomer typically contains a functional groupcapable of reacting with an amino functional group.

The vinyl-polymerizable unsaturated, hydrolyzable silanes used in thisinvention contain at least one silicon-bonded hydrolyzable group, suchas, for example, alkoxy, halogen, and acryloxy, and at least onesilicon-bonded vinyl-polymerizable unsaturated group such as, forexample, vinyl, gamma-methacryloxypropyl, alkenyl gamma-acryloxpropyl,6-acryloxyhexyltriethoxysilane, alkyloxypropyl, ethynyl, and 2-propynyland preferably is an ethylenically unsaturated group. Any remainingvalances of silicon not satisfied by a hydrolyzable group or avinyl-polymerizable unsaturated group being satisfied by a monovalenthydrocarbon group, such as, for example, methyl, ethyl, propyl,isopropyl, butyl, pentyl, isobutyl, isopentyl, octyl, decyl, cyclohexyl,cyclopentyl, benzyl, phenyl, phenylethyl, and naphthyl. Suitable silanesof this type include those represented by the formula:

R_(a)SiX_(b)Y_(c)

wherein R is a monovalent hydrocarbon group, X is a silicon-bondedhydrolyzable group, Y is a silicon-bonded monovalent organic groupcontaining at least one vinylpolymerizable unsaturated bond, a is aninteger of 0 to 2, preferably 0; b is an integer of 1 to 3, preferably3; c is an integer of 1 to 3, preferably 1; and a+b+c is equal to 4.

Suitable vinyl polymerizable unsaturated hydrolyzable silanes that canbe used in this invention include, but are not limited to,3-acryloxypropyltriethoxysilane, ethynyltriethoxysilane,2-propynyltrichlorosilane, 3-acryloxypropyidimethylchlorosilane,3-acryloxypropyidimethylmethoxysilane,3-acryloxypropylmethyldichlorosilane, 3-acryloxypropyltrichlorosilane,3-acryloxypropyltrimethoxysilane, allyldimethylchlorosilane,allylmethyldichlorosilane, allyltrichlorosilane, allyltriethoxysilane,allyltrimethoxysilane, chloromethyidimethylvinylsilane,[2-(3-cyclohexenyl)ehtyl]dimethylchlorosilane,2-(3-cyclohexenyl)ethyltrimethoxysilane, 3-cyclohexenyltrichlorosilane,diphenylvinylchlorosilane, diphenylvinylethoxysilane,(5-hexenyl)dimethylchlorosilane, (5-hexenyl)dimethylchlorosilane,5-hexenyltrichlorosilane, methacryloxpropyldimethylchlorosilane,3-methacryloxypropyidimethylethoxysilane,3-methacryloxypropylmethyldiethoxysilane,3-methacryloxypropyltrichlorosilane,methyl-2-(3-cyclohexenyl)ethyldichlorosilane,methyl-3-(trimethylsiloxy)crotonate, 7-octenyltrichlorosilane,7-octenyltrimethoxysilane, 1-phenyl-1-trimethylsiloxyethylene,phenylvinyldichlorosilane, styrylethyltrimethoxysilane,13-tetradecenyltrichlorosilane, 4-[2-(trichlorosilyl)ethyl]cyclohexene,2-(trimethylsiloxy)ethylmethacrylate, 3-(trimethylsilyl)cyclopentene,vinyldimethylchlorosilane, vinyldimethylethoxysilane,vinylethyldichlorosilane, vinylmethyldiacetoxysilane,vinylmethyldichlorosilane, vinylmethyldiethoxysilane,vinyltrimethylsilane, vinyltrichlorosilane, vinyltriethoxysilane,vinyltrimethoxysilane, vinyltris(beta-methoxyethoxy)silane,vinyltriacetoxysilane, 3-methacryloxypropyltrimethoxysilane, and3-methacryloxypropyltris(beta-methoxyethoxy)silane.

The preferred silane compounds are vinyltrichlorosilane,vinyltriethoxysilane, vinyltrimethoxysilane,vinyltris(beta-methoxyethoxy)silane, vinyltriacetoxysilane,3-methacryloxypropyl trimethoxysilane,3-methacryloxypropyltris(beta-methoxyethoxy)silane, and mixturesthereof. These compounds are preferred due to commercial availability,ease of use, as well as good polymer property improvement.

The radically polymerizable unsaturated grafting compound also can be acarboxylic acid or an anhydride thereof, with about three to about 10carbon atoms, with preferably at least one olefinic unsaturation, andderivatives thereof. Examples of the carboxylic acid and anhydrideinclude, but are not limited to, an unsaturated monocarboxylic acid suchas acrylic acid or methacrylic acid; an unsaturated dicarboxylic acidsuch as maleic acid, fumaric acid, itaconic acid, citraconic acid, allylsuccinic acid, mesaconic acid, glutaconic acid, Nadic acid(norbornene-2,3-dicarboxylic acid), methyl Nadic acid,tetrahydrophthalic acid, or methylhexahydrphthalic acid; an unsaturateddicarboxylic anhydride such as maleic anhydride, itaconic anhydride,citraconic anhydride, allyl succinic anhydride, glutaconic anhydride,Nadic anhydride (norbornene-2,3-dicarboxylic anhydride), methyl Nadicanhydride, tetrahydrophthalic anhydride, or methyltetrahydrophthalicanhydride; or a mixture of 2 or more thereof. Of these unsaturatedcarboyxlic acids and acid anhydrides thereof, maleic acid, maleicanhydride, Nadic acid, methyl Nadic acid, methyl Nadic anhydride, orNadic anhydride is preferably used. The most preferred anhydride ismaleic anhydride.

The quantity of graftable functional monomer used in the processaccording to the invention depends on the properties which it isintended to obtain in the grafted polyolefin, the quantity ofradical-generator used and the residence time of the mixture in thereactor. It is generally sufficient to permit an improvement in theproperties of the grafted polyolefin obtained. In practice there is nointerest in using an excessive quantity because any excess beyond thequantity needed to obtain the maximum degree of grafting does not bringabout any improvement in the finished product. The quantity is usuallyat least 0.01 part to 20 parts by weight per 100 parts by weight ofpolyolefin; it is preferably at least 0.1 part to 17 parts by weight;and most preferably 1 part to 15 parts by weight per 100 parts ofpolyolefin. Values of at least 10 parts by weight are the mostcommonplace. In general the quantity does not exceed 20 parts by weightper 100 parts by weight of polyolefin; in most cases it does not exceed17 parts by weight, with values not exceeding 15 parts by weight beingthose most recommended.

The other reactive component used in the practice of the presentinvention is an amino carboxylic acid and more preferably an aminopolycarboxylic acid. Typically, the amino carboxylic acid has theformula HNR₂ or H₂NR wherein R is a carboxy functionalized aliphaticgroup containing 1-8 carbon atoms. The R group can also be a carboxyfunctionalized aromatic group such as aryl or naphthyl. Illustrativenon-limiting examples of the amino carboxylic acids include glycine,glycylglycine, alanine, valine, leucine, isoleucine, phenylalanine,tyrosine, proline, hydroxyproline, serine, threonine,3-amino-3-methylbutanoic acid, 6-aminocaproic acid, aminobenzoic acid(meta and para), 4-aminosalicylic acid, iminodiacetic acid, lanthionine,methionine, aspartic acid, glutamic acid, lysine, delta-aminolevulinicacid, beta-alanine, alpha-aminobutyric acid, gamma-aminobutyric acid,gamma, epsilon-diaminopimelic acid, gamma, alpha-diaminobutyric acid,ornithine, omega-aminododecanoic acid, beta-cyanoalanine,epsilon-methylhistidine, canavanine, djenkoic acid, 1-azaserine,gamma-methylene glutamic acid, N-methyl tyrosine, arginine, tryptophan,norvaline, cystine, cysteine, imidazole-4,5-dicarboxylic acid andhydroxylysine. The preferred amino carboxylic acid is an aminopolycarboxylic acid with iminodiacetic acid being the most preferred.Other amino polycarboxylic acids that can be used are selected from thegroup consisting of beta-alanine diacetic acid, ethylene diaminetriacetic acid, diethylene triamine pentaacetic acid, trans-1,2-diaminocyclohexane triacetic acid.

The amount of the amino carboxylic acid or a salt thereof that is usedin the present invention depends on the level of final functionalitythat is desired for a given industrial application. In the case wherethe polyolefin is first grafted with a the reactive unsaturated monomer,the amount used is at least sufficient to functionalize 50% of thereactive groups. For example, in the case of a maleic anhydride graftedpolyolefin, at least one mole of amino carboxylic acid per graftedanhydride moiety is used. Of course, the full stoichiometric amount ofamino polycarboxylic acid can be used to fully react all of the graftedanhydride moieties.

When the amino carboxylic acid or its salt is grafted directly, thequantity of graftable material used in the process according to theinvention depends on the properties which it is intended to obtain inthe grafted polyolefin, the quantity of radical-generator used and theresidence time of the mixture in the reactor. It is generally sufficientto permit an improvement in the properties of the grafted polyolefinobtained. In practice there is no interest in using an excessivequantity because any excess beyond the quantity needed to obtain themaximum degree of grafting does not bring about any improvement in thefinished product. The quantity is usually at least 0.01 part to 20 partsby weight per 100 parts by weight of polyolefin; it is preferably atleast 0.1 part to 17 parts by weight; and most preferably 1 part to 15parts by weight per 100 parts of polyolefin. Values of at least 10 partsby weight are the most commonplace. In general the quantity does notexceed 20 parts by weight per 100 parts by weight of polyolefin; in mostcases it does not exceed 17 parts by weight, with values not exceeding15 parts by weight being those most recommended.

The polyolefins used in the instant invention include but not limited topolypropylene homopolymer and copolymer, polyethylene homopolymer andcopolymer(including low density products to high density products),poly-1-butene homopolymer and copolymer, poly4-methyl-1-pentenehomopolymer and copolymer, ethylene-propylene copolymer elastomer,propylene-1-butene copolymer resin or elastomer, andpropylene4-methyl-1-pentene copolymer resin or elastomer. Among them,the preferred starting material for the production of modified productsis polybutylene.

The polybutylene referred to herein is one butene-1 polymer containingfrom 80% preferably from 95% and more preferably from 97% by weight ofisotactic portions. The weight average molecular weight may range fromabout 10,000 to about 1,000,000; determined by gel permeationChromatography. Suitable poly-1-butene also have a density of from 0.875to 0.925, preferably from 0.900 to 0.920 and most preferably from 0.910to 0.915. Suitable poly-1-butenes have melt indices in the range of from0.1 to 5,000, preferably from 0.1 to 200, more preferably from 0.4 to20, and most preferably from 1.0 to 5 dg/min, as determined by ASTMD-1238 Condition E, at 190° C. The intrinsic viscosity of thepoly-1-butene may range from 0.07, preferably from 7 at 130° C. in“decalin” (decahydronaphthalene).

These poly-1-butene polymers including their methods of preparation, andtheir properties are known in the art. An exemplary reference containingadditional information on polybutylene is U.S. Pat. No. 4,960,820 whichis herein incorporated by reference.

A poly-1-butene polymer (PB) usable herein is either a butene-1homopolymer or a copolymer or a terpolymer. If a butene-1 copolymer isused, the non-butene comonomer content is from 1 to 50 mole %,preferably from 1 to 30 mole % of either ethylene, propylene, or analpha olefin having from 5 to 8 carbon atoms. The poly-1-butenes can bemodified to increase surface activity by reaction with, for example,maleic anhydride.

Suitable poly-1-butenes can be obtained, for example, in accordance withZiegler-Natta low-pressure polymerization of butene-1, e.g. bypolymerizing butene-1 with catalysts of TiCl₃ or TiCl₃—AlCl₃ andAl(C₂H₅)₂Cl at temperatures of 10-100° C., preferably 20-40° C., e.g.according to the process described in DE-A-1,570,353. It can also beobtained, for example by using TiCl₄—MgCl₂ catalysts. High melt indicesare obtainable by further processing the polymer by peroxide cracking,thermal treatment or irradiation to induce scissions leading to a highermelt flow material.

Duraflex.R. DP0200, a polybutylene polymer produced by Shell ChemicalCompany, of Houston, Tex. is a particularly suitable polymer. Thispolymer is a homopolymer with a melt index of 2.0 g/10 min. at 190° C.and 2.16 kg and a weight average molecular weight of 439,000.

Further polybutylene polymers and copolymers that are useful in makingthe new grafted polymers of the present invention are those disclosed inU.S. Pat. Nos. 4,568,713; 5,594,074 and 5,847,051 whose entire contentsare incorporated by reference herein.

The graft reaction is preferably carried out in a melt processingreactor such as single or multiple screw extruders, rubber masticators,Banbury processors, Brabender processors, roll-mills and the like.

In carrying out the grafting process of the present invention, theethylenically unsaturated monomer and peroxide reagents should be mixedwith the polyolefin preferably before the polyolefin is heated, and mostpreferably the ethylenically unsaturated monomer and the peroxide freeradical initiator should be mixed prior to adding such mixture to thepolyolefin. Although use of a solvent is not required for mixing thereagents with polyolefin, using an inert, low molecular weight, volatilesolvent, such as pentane, hexane, or other hydrocarbons, or methylethylketone, acetone, or other low molecular weight species, or any othersuitable liquid, to coat the polymer with the reagents, can improve themixing of the reagents and improve the dispersion of the reagent mixtureon the polyolefin when so used. The mixture of peroxide initiator andethylenically unsaturated monomer is added to the polyolefin to coat thepolymer with such components of the mixture. If a solvent is used as acoating and dispersion aid for the reagents, after the mixture is coatedonto the polyolefin the solvent is evaporated from the polymer, leavingthe ethylenically unsaturated monomer and peroxide reagents on thesurface of the polyolefin.

The reaction temperature for practicing the invention are typically inthe range of 125-250° C. Good results are obtained at temperatures ofabout 180-230° C., but preferably 180-220° C. The longer the time thatthe polyolefin is subjected to the reaction temperature, namely thepreferred temperature of 180-220° C., the greater will be the amount ofgrafted ethylenically unsaturated monomer, without further degrading themolecular weight of the polyolefin.

In the first preferred embodiment of the invention, the new polymers ofthe instant invention are made by the method shown in scheme 1. As shownin scheme 1, polybutylene is first grafted (step 1) with maleicanhydride using a free radical initiator such as a peroxide. Subsequentto the maleation step, the grafted polymer is reacted with iminodiaceticacid to give a polymer having two or more functional moieties pergrafting site whether one uses one or more moles of iminodiacetic acid.

Although applicants does not wish to be bound to any theories ormechanisms, it was assumed that iminodiacetic acid prefers to react onlywith the acid groups of maleated polybutylene, but in fact the reactionis random. The iminodiacteic can also react with active tertiary carbonsas shown in scheme 2. Applicants have calculated that in a 5% maleatedpolybutylene molecule of a million molecular weight unit there could beapproximately 300 potentially active carbon atoms per maleic moleculegrafted to the polybutylene backbone, thus providing substantially moreactive carbon for which the iminodiacteic acid can react. It is alsopossible that maleic anhydride may also be grafted onto the secondarycarbon atoms of the polybutylene backbone.

In the second preferred embodiment as shown in scheme 2, thepolybutylene is directly grafted with the iminodiacetic acid also usinga peroxide free radical initiator. The peroxide generates free radicalsthat initiate the site for reaction with iminodiacetic acid yielding twoacid groups per grafting site. The iminodiacetic acid is grafted ontothe tertiary carbon atoms of the polybutylene backbone. It is alsopossible that the iminodiacetic acid may also be grafted on to thesecondary carbon atoms of the polybutylene backbone.

In the third preferred embodiment shown in scheme 3, an adduct of maleicanhydride and iminodiacetic acid is preformed and then reacted with viaperoxide free radical grafting with the polybutylene. It should be notedthat the preformed adduct can also be made with the acid or esterinstead of the anhydride. The resulting adduct can have carboxamidebonds as well as acid-base adduct bonds depending on whether the adductis further heated to generate the carboxamide bonds.

There are certain advantages to adduct formation prior to grafting. Thereaction sequence can be discussed as follows: In a two to one moleration of iminodiacetic to maleic anhydride the first mole ofiminodiacetic acid can react to form an amide linkage (carbonyl-nitrogenbond). The second mole reacts with the acid moiety to form an ionic bondwith the nitrogen forming the quaternary nitrogen. Under vacuum and heatone can force the reaction to continue by distilling one mole of waterper mole of iminodiacetic acid (condensation), thus forming a moleculethat has four carboxylic acid groups attached to the maleic anhydridevia amide bonds.

Adduct formations shown in scheme IIII can be accompanied by theformation of dimers (see below) and trimers of the adduct. The ratio ofmonomer to dimer to trimer can be controlled by the reaction conditions(temperature and reaction time), addition of Lupersol 101, as well asuse of the salt form of the iminodiacetic acid to form the monomer.

The adduct dimer is formed by reaction of one of the pendant acid groupsof a monomer adduct with the α, β unsaturated amino functionality ofanother monomer adduct. This acid catalyzed nucleophilic addition ofheteroatoms to an α, β unsaturated carbonyl group is an example of theMichael addition reaction. This addition reaction is facilitated by thepresence of the acid groups, high temperature and long reaction times.However, it should be noted that dimer and trimer adduct formation canbe significantly minimized, if desired, by neutralization of theiminodiacetic acid prior to reaction with any base, or by use of thesalt (e.g. sodium, potassium salts) of the iminodiacetic acid in theinitial adduct formation. This prevents the Michael addition reaction,because the carboxylate anion does not readily add to an α, βunsaturated carbonyl group.

Next is the compound obtained by following the same reaction sequence asfor the dimer but adding up to 2500 ppm of Luppersol 101 before heatingthe mixture. Trimer formation:

The method illustrated in scheme 3 is used to further enhance thefunctionality of the adduct. For example, since the nitrogen atoms ofthe iminodiacetic is basic it should react with acid groups of theadduct molecule. Therefore, three moles of iminodiacetic acid added toone mole of maleic anhydride can react under heat and vacuum to formfive acid groups etc. The resulting structure can look like a dendrite.It is also conceivable that by using an acid catalyst and adjusting thereaction conditions one could form a oligamer>(100)n having the basicstructural of the dimer or trimer, but still maintain the olefinic groupof the maleic anhydride that is needed for the grafting to the polymerbackbone. The grafting of a pre-formed adduct containing multiplesfunctional groups of carboxylic acid to the polymer's backbone wouldprovide means to achieve high levels of polarity to the polybutylenepolymer.

The polyfunctional polyolefin compositions of this invention can bebonded to a polar material by heating at least the multifunctionalpolyolefin composition to melt, and then joining them together,preferably under pressure. For example, when the polar material is notthermoplastic, there can be employed a method which comprises coating orlaminating a molten polyfunctional polyolefin composition onto the polarmaterial; a method comprising superimposing both together, and thenmelt-bonding them under heat; a method comprising adhering thepolyfunctional polyolefin composition to the polar material byelectrostaticity and then melting the polyfunctional polyolefincomposition to laminate it on the polar material; and a methodcomprising heating the polar material to a temperature above the meltingpoint of the polyfunctional polyolefin composition, and then adheringthe polyfunctional polyolefin composition thereto and simultaneouslymelting it. Where the polar material is thermoplastic, there can be useda method which comprises melting both the polyfunctional polyolefincomposition and the polar material and coextruding and laminating them,and a method which comprises coating or laminating the moltenpolyfunctional polyolefin composition onto the polar material.

Although pre-treatments of one or both surfaces of the adherents, suchas a flame treatment, a corona discharge treatment, and/or coating of aprimer, are not required in bonding the polyfunctional polyolefincomposition of this invention to polar materials, the adherents may beso treated, if desired.

Several batches of polyfunctional polybutylene were made and evaluatedto test whether the increased polarity of polybutylene offers aperformance advantage as well as diversity in end use applicationcompared to other functionalized or non-functionalized polymers.

When the polyfunctional polyolefin composition of this invention isbonded to polar materials, both initial adhesiveness and durableadhesiveness can be enhanced over the case of using polyfunctionalpolyolefins graft-modified with unsaturated carboxylic acids or theirderivatives. Hence, the laminates or composites obtained can be used forlong periods of time under more severe service conditions. Thecomposition of this invention finds many uses such as rustproof coatingsor hot melt adhesives for metal tubes or plates, and laminate orcomposite films and sheets, and containers, tubes and bottles which areuseful as packaging materials for foods, liquids, and medicines. Theadhesive properties of the polyfunctional polybutylene of the presentinvention are summarized in Table 1.

TABLE 1 PROPERTIES OF MODIFIED POLYBUTYLENE IN ADHESIVES 03TAG001LR20878-52 LR20878-90 LR20878-91 I.D. NO. PB8910 PC PB8910 PC + PB8910PC + PB8340 + (MODIFIED) POLYMER NEAT Acrylic Acid MA-IDA MA-IDA LAPSHEAR, psi Steel to Steel 133 430 508** 1320 Aluminum to Aluminum 38 142415** 1540 PVC to PolyVinylChloride 67 91 240 n/a G-10¹ to G-10 118 430498 n/a HDPE to HDPolyEthylene n/a n/a  50 n/a PS to PolyStyrene n/a n/a119 n/a PP to PolyPropylene n/a n/a 300 n/a S.A.F.T.(1 Kg) ° C. 89 n/a 84 n/a Viscosity @177° C.,cps 650-1050 600 n/a n/a Softening Point,° C.n/a n/a Grafted Moiety: % w acrylic acid 0 11.4  0 0 % w maleicanhydride 0 0  6 6 % w iminodiacetic acid 0 0  12 12 Steel and aluminumpreheated to 50° C. **Not preheated to 50° C. Resins applied at 182° C.Crosshead speed was 12 inches/minute. ¹Meets N.E.M.A. FR-4 Requirements8910 PC-6% w ethylene 8340-0.75% w ethylene

The data reported in Table 1 were obtained without any special surfacetreatment for the aluminum or the stainless steel with the exception ofwiping the metal surfaces with isopropanol to remove grease or surfacecontamination. It is clear that the polybutylene materials which werefurther modified with iminodiacetic acid, particularly the modified 8340grade polymer, have substantially better adhesion to steel and aluminumcompared to the acrylated grafted polybutylene polymer as well as thenon-modified polymer. There is also ample evidence from this data thatuseful levels of strong adhesion can be achieved with a variety of polarand non-polar polymeric substrates. This coupled with the peel strengthdata in Table 2 shows the clear advantage, which can be achieved inselected polybutylene materials with the free radical grafting ofiminodiacetic acid.

TABLE 2 PEEL STRENGTH ON ALUMINUM % *PEEL % % Acrylic RESIN ID. NO.lbs/in. Maleic IDA acid PB8910 PC(control) 20878-68-1 0.064 0 0 0 PB8910PC(1:1) 20878-68-3 2.98 6 6 n/a PB0800 (1:2) 20878-73 3.29 6 13.9 n/aPOLYBOND(1001) lot #0A50008 4.79 n/a ˜5 PB8910 PC(1:2) 20878-75 7.09 615.4 0

TABLE 3 LAP SHEAR PROPERTIES OF MODIFIED POLYBUTYLENE BY PRE-FORMEDADDUCT ADDITION LR20878- I.D. NO. 105-1 LR20878-105-3 BASE RESIN PB8340PB8340 % OF MALEIC ANHYDRIDE ˜7.0 ˜6.0 % OF IDA 0.0 ˜15.9 Lap shear, psi1226 1911

In a fourth preferred embodiment, the functionalized polybutylene of thepresent invention can be processed under high shear in a mixture ofwater and a suitable surfactant and can be made into a film formingemulsion. Coating from these emulsions has lower undesirable volatilecomponents than solvent borne coating. The superior functionalizedpolybutylene is suitable for several new application such as for hotmelt adhesives and for emulsions. Applicants have discovered a newmethod, which extends the state of the art beyond that of maleicanhydride grafting and yields improved functionality in polybutylene.This method results in the grafting of a small molecules ofbi-functional n-substituted diacids to a maleic anhydride which can begrafted to polybutylene. The small chelate, iminodiacetic acid (IDA),because it is very reactive and can coordinate with most metals to formstable structures. The increased functionality of the grafted polymerprovides higher adhesive strength in adhesive joints in a number ofdifferent substrates.

The emulsion are typically made by mixing together at least one graftedpolyolefin, water and emulsifying agent to form a mixture. The materialsare then stirred under high shear conditions at an effective temperatureto achieve proper emulsification.

The emulsions prepared according to the present invention generallycontain 25 to 55 weight percent of grafted polyolefin, with a weightpercent of grafted polyolefin of 40-55% being the most preferred.

Exemplary of the emulsifying agents, whether used alone or in admixture,are the traditional anionic agents such as the alkali metal salts offatty acids, alkyl sulfates, alkylsulfonates, alkylarylsulfonates,sulfosuccinates, alkyl phosphates, abietic acid salts, whether or nothydrogenated, nonionic agents such as polyethoxylated fatty alcohols,polyethoxylated and optionally sulfated alkylphenols, polyethoxylatedfatty acids, etc. The emulsifying agents are advantageously employed ina proportion of 0.1% to 10% by weight relative to the total weight ofthe grafted polyolefin. The most preferred amount of surfactant oremulsifying agent is 3 to 8%.

The amount of water in the emulsion generally varies, depending upon thedesired concentration, but is generally between 50-80 weight percent,preferably between 55-80 weight percent and most preferably between 60and 75 weight percent.

Applicants have synthesized emulsions based on the grafted products ofthe present invention. Two emulsions were prepared, one containinggrafted acrylic acid and the other one containing the adduct of maleicanhydride with iminodiacetic acid. The properties of the emulsions aresummarized in Table 4.

TABLE 4 EMULSION PRODUCT CHARACTERISTICS LR20878- LR20878- I.D. NO. 129130 BASE RESIN PB8910 PB8910 % OF MALEIC ANHYDRIDE 0.0 ˜6.0 % OF IDA 0.0˜16.3 % ACRYLIC ACID 12 0.0 TOTAL SOLIDS 50.5 49.0

Glue from emulsions of functionalized PB or PP can be made quite easily.The carboxylic acid groups attached to the polymer's backbone can reactreadily with bases such as hexamethyldiamine etc. to cross-link andreduce set-up time.

The grafted polyolefins of the instant invention can be used in thefollowing additional industrial applications:

(1) Thermoset resins wherein a water soluble amine such ashexamethylenediamine reacts with the carboxylic acid portions of thepolymer to cross-link under curing conditions.

(2) Hot melt adhesives as shown in Table 1.

(3) The grafted polyolefins can be blended with other polar engineeringresins and act as coupling or compatibilizer to improve processability.They can also be blended with polar tackifying resins as well as othernonpolar olefinic polymers as adhesion promoters.

(4) The grafted polyolefins can be used in extrusion processes toprepare tie-layers in multilayer constructions with other polymers, suchas PB/tie-layer/polyamide.

(5) The grafted polyolefins of the present invention can also beconverted into ionomers by neutralization with bases such as ZnO orMg(OH)₂.

EXAMPLE 1 Preparation of Acrylated Polybutylene: 11.4% by Weight I.D.No.: LR20878-52

The equipment used to conduct this preparation is a two-liter glassvessel with three female 24/40 joints. One inlet is fitted with achilled condenser, a second inlet set-up with a mechanical stirrer and athird inlet has a thermocouple probe to measure melt temperature. Thereaction is conducted under a nitrogen blanket and the reactor vesselplaced inside a heating mantle (Glas-Cole) temperature controlled withEurotherm model 847. The starting materials are polybutylene ( having aviscosity of 6,000 to 15,000 and designated as PB 8910 PC; and acrylicacid monomer, neat obtained from Aldrich Chemical.

To the glass vessel reactor there is added 270 g of PB8910 PC and thetemperature is raised to 120° C. Once the temperature is stabilized stirat a constant 50 rpm for 15 minutes. Add slowly 33 ml of acrylic acid tothe melt and stir at 50 rpm for 15 min. Raise the temperature slowly(1-2° C./min) to 205° C. and stir for an additional 15 minutes.

The resulting product is then poured into a Teflon® coated pan andallowed to cool. The product did not exhibit monomer odor.

EXAMPLE 2 Polyfunctionalized Polybutylene: 12% W of Iminodiacetic AcidI.D. No.: LR20878-90

The reactor vessel and setup for this example is identical to that ofExample 1. The Chemicals used are: a polybutylene identical to the oneused in Example 1 (PB 8910 PC) Maleic Anhydride, briquettes 99%, fromAldrich Chemical Co., Iminodiacetic Acid, free acid 97%, ICN andLupersol 101, neat.

To the glass vessel there is added 564g of PB8910 PC and the temperatureis raised to 110° C. while maintaining a nitrogen blanket and stirringgently at 50 rpm. Add slowly 0.12 ml of neat Lupersol 101 whilestirring. Under a nitrogen blanket add slowly 36 g (0.367 moles) ofmaleic anhydride and keep stirring until maleic anhydride has completelydispersed and melted. Stir for an additional 10 minutes and whilemaintaining a nitrogen blanket add slowly 82.9 g (2×0.367 moles) ofiminodiacetic acid(IDA). Stir until the IDA has dispersed and slowlyraise the temperature (1-2° C./min) to 210° C. Gassing is observed,maintain temperature and stirring (50 rpm) until gassing subsides (10minutes). Torque was measured to be 70-90 oz-in at 50 rpm. The productis poured into Teflon® coated pans and allow cooling.

EXAMPLE 3 Polyfunctionalized Polybutylene: 12% W of Iminodiacetic AcidI.D. No.: LR20878-91

The reactor vessel and setup for this example is identical to that ofExample 1. The Chemicals used are: a polybutylene identical to the oneused in Example 1 (PB 8910 PC) Maleic Anhydride, briquettes 99%, fromAldrich Chemical Co., Iminodiacetic Acid, free acid 97%, ICN andLupersol 101, neat.

Add 564 g of PB 8340 to a reactor vessel which was pre-purged withnitrogen and also preheated to 125° C. Allow the pellets to melt andbegin stirring at 4 rpm. Add 2.54 ml of Lupersol 101 and stir until theperoxide is dispersed. Add 36 g of maleic anhydride while maintaining anitrogen blanket

The addition of IDA was done in two steps:

Step 1.

The temperature was raised to 180° C. and half (˜41.45 g) of the IDA isadded to the mixture slowly while maintaining a nitrogen environment.Stir to disperse the IDA.

Step 2.

Add the rest of the IDA to a total of 82.9 g and raise the temperatureto 210° C. and stir for 18 minutes. No out-gassing observed. Torque wasmeasured at about 310 oz-in at 17 rpm. The product is poured into aTeflon® coated pan and allowed to cool.

EXAMPLE 4 Preparation of the Pre-Formed Adduct LR20878-122 Large Batch

Into a three necked flask there is added 100 g of maleic anhydride and271.36 g of iminodiacetic acid. Stir at 50 rpm and gently purge withdried nitrogen. Provide a reflux tube and a positive nitrogen gas flowwhile raising the temperature slowly to 200° C. Pull a vacuum andcollect condensate. Pour the product into Teflon® coated pan and allowto cool.

EXAMPLE 5 Synthesis of Acrylated Polybutylene ID.NO. LR. 20878-119

The reaction was processed in a 2 gallon stainless steel autoclave Parrreactor with computer pressure and temperature control. The reactor wascleaned and assembled with the reactor bottom drain valve pointed towardthe front of the reactor stand.

1496.0 g of Polybutylene polymer (solid beads, 87.91% of the totalreactants) was directly poured into the open reactor and the reactor wassealed. The reactor was pressurized to 50 psig with chromatographicnitrogen, the pressure was released and the reactor was pressurized foranother two times. The reactor was purged with nitrogen at about 3liter/minute for 20 minutes to remove oxygen and moisture, the reactorwas then closed with nitrogen shut off; and heating was started. ThePolybutylene was heated to 120° C. and melted. Stirring was started andthe speed was 50 rpm. Nitrogen was purged at about 1 liter/min atatmospheric pressure inside the reactor. At 124° C. 1.70 g of freeradical initiator Lupersol 101 (liquid, 1000 ppm of the total reactants)was added by injecting into the reactor through the pressure gaugemanifold using a glass syringe, the pressure gauge was put back on thereactor and sealed with Teflon® tape. Nitrogen was pressurized into thereactor to 50 psig and released to remove any oxygen and moistureintroduced into the reactor during the initiator addition. Nitrogen wasclosed and the initiator was stirred into the liquid polymer.

The reactor temperature was equilibrated at 133° C., nitrogen was purgedagain at about 1 liter/min at atmospheric pressure inside the reactor.The stirrer speed was 60 rpm. 204 g of acrylic acid (liquid, 11.99% ofthe total reactants) was added at about 133° C. into the reactor bypouring it through the pressure gauge manifold in three minutes, using anarrow-stem glass funnel. Cool acrylic acid solidified the polybutyleneregionally and caused the stirring to stop. It was later discovered thatthe dip tube inside the reactor was bent. The dip tube was replaced, thereactor was reassembled and purged with nitrogen for 5 minutes beforethe temperature exceeded 140° C. and the reaction was continued. Thestirrer speed was increased to 290 rpm.

The heater set point of the reactor was increased to 200° C. with thetemperature controller set point at 60-80%. The reactor was pressurizedto 50 psig and the reactor was heated at a rate of about 1.5° C./min.When the temperature reached 200° C., timing was started. The reactionwas fast and was completed in 12 minutes at 200-210° C.

The product removal was immediately prepared; it included with heatingthe bottom ram drain valve with a heat gun and positioning twoTeflon®-lined drain pans under the reactor drain. After 10 minutesexpired, the bottom drain valve was immediately opened and the reactorwas pressurized to 100 psig with nitrogen to remove the product at 210°C. The nitrogen inlet valve was shut off when the reactor pressurereached 100 psig.

The reaction product, 10-12% functionality of acrylated polybutylene,was white, strong-sticky solid polymer at room temperature; it shrunk inice-water and could be peeled off from the Teflon®-lined drain pans. Theproduct has approximately the following physical properties: mp 90° C.,viscosity 700 cP at 177° C.

The resulting acrylated polybutylene was cryogenically grounded and theparticle size for each kind of ground samples was 200-1000 μm under 400×optical microscope.

EXAMPLE 6 Synthesis of Polyfunctional Polybutylene ID. NO. LR 20878-120

Before the synthesis reaction, 1500 g of polybutylene was used to washdown 10 the reaction residue from Example 3 at 120-130° C. (stirred at120° C., 300 rpm for 30 minutes, mixture was drained out at 120° C. at100 psig). Safety precautions were taken.

The reaction was also processed in a two gallon stainless steelautoclave Parr reactor with computer pressure and temperature control.After the reactor was cleaned-up with polybutylene, the bottom drainvalve was closed. 1321.0 g of Polybutylene polymer (77.63% of the totalreactants) was poured into the reactor through the rupture disk portusing a plastic funnel, the reactor was sealed with no gas leaking. Thereactor was pressurized to 50 psig with chromatographic nitrogen, thepressure was released and the reactor was pressurized for another twotimes. The reactor was purged with nitrogen at about 3 liter/minute for20 minutes to remove oxygen and moisture. Just before the passage of 20minutes purging time, the reactor was closed and heating was started.

The polybutylene was heated to 120° C. and melted. Stirring was startedand the speed was 50 rpm. Nitrogen was purged at about 1 liter/min, atatmospheric pressure inside the reactor. When the temperature reached135° C., 1.7119 g of the free radical initiator Lupersol 101 (1006 ppmof the total reactants) was added by injecting it into the reactorthrough the pressure gauge manifold using a glass syringe with stirringspeed 160 rpm, the pressure gauge was put back on the reactor sealedwith Teflon® tape. Nitrogen was pressurized into the reactor to 50 psigand released to remove any oxygen and moisture introduced into thereactor during the initiator addition. Nitrogen was closed and theinitiator was stirred into the liquid polymer.

The temperature was up to 150° C. and the reactor was kept at thistemperature, nitrogen was purged again at about 2 liter/min. atatmospheric pressure inside the reactor. 379 g of maleic anhydridederivative with iminodiacetic acid (yellow powder, 22.28% of the totalreactants). The adduct was identified as 20878-120A. The adduct wasadded by pouring it through the rupture disk port using a plastic funnelin 15 minutes, the reactor was closed with nitrogen shut off; heatingwas continued and the stirring speed was increased to 296 rpm.

The heater set point of the reactor was increased to 200° C. with thetemperature controller set point at 60-80%. The reactor was pressurizedto 50 psig and the reactor was heated at a rate of about 5° C./min. Whenthe temperature reached 200° C., timing was started, the reaction wasfast and was completed in 10 minutes at 200-210° C. The product removalwas immediately prepared as the same as for synthesis of Example 5.After 10 minutes have expired, the bottom drain valve was immediatelyopened and the reactor was pressurized to 60 psig with nitrogen toremove the product into two Teflon®-lined drain pans at 210° C. Thenitrogen inlet valve was shut off when the reactor pressure reached 60psig.

The reaction product, polyfunctional polybutylene, was a yellowstrong-sticky solid polymer at the room temperature; it shrunk inice-water and could be peeled off from the Teflon® lined drain pans.

The resulting functionalized polybutylene was cryogenically grounded andthe particle size for each kind of ground samples was 200-1000 μm under400× optical microscope.

EXAMPLE 7 Emulsification of Acrylated Polybutylene ID NO 20878-128

A 14 speed Osterizer blender (maximum 1100 ml volume) was used toemulsify the ground acrylated polybutylene.

539.42 g of distilled ionized water (49.04% of the total reactants) wascharged into a 1.0 liter beaker, 66.0 g of surfactant No.23W004 (acolorless, viscous liquid provided by Shell Chemical Company atWesthollow Research Center, Houston, Tex.; 6% of the total reactants)was added slowly into the beaker while stirring. The surfactant-watermixture was poured into the blender.

494.58g of the sample (ID. NO. LR. 20878-119) of mono-functionalacrylated polybutylene (white powder, 44.96% of the total reactants) wascharged into the blender by portions. After each portion was poured intothe blender, the blending was turned on, and the stirring was quicklyincreased to the highest speed. Vigorous stirring prevented the mixedmaterial from agglomeration. “Pulse” function on the blender was used torelease air bubbles inside the mixture after each time of stirring. Ittook 1 hour to emulsify all the acrylated polybutylene into white milkywater mixture, the highest temperature reached inside the blender whileblending the mixture was 53° C.

The product particle size was mostly in the range of 20-40 μm with verysmall number of oversized particles. The particle size was analyzedusing 400× Bausch & Lomb optical microscope. The viscosity of theproduct was 1275 centipoise at room temperature, which compares wellwith the expected value (greater than 1000 centipoise).

Homogenization was attempted by using a HC-8000 3A sanitary pneumaticmicrofluidizer from the Microfluidics International Corporation. Themicrofluidizer was modified to stand 75 psig in line nitrogen pressureand 120° C.-130° C. fluid temperature, and it can reduce the particlesize repeatedly with 9000 psig highest pressure even it was designed for8000 psig maximum.

The microfluidizer was assembled and cleaned. The air pump was primedusing distilled ionized water at 15 psig dry air pressure. The pump wasprimed until no air bubbles were observed. Pure water was used to testthe working condition of the microfluidizer with air pressure set up at110 psig, constant 4000-5000 psig pressure in line in front of thehomogenizer module was observed during the test. Temperature rise-up inthe homogenizer module was approximately 1.5° C./1000 psig.

The feed reservoir was wrapped with heating tape controlled by a variac,and the reservoir was heated to 65° C. The warm (53° C.) emulsifiedpolybutylene was immediately poured into the warm feed reservoir, thenthe air control valve was opened, homogenization was started. A smallstream of the homogenized polymer was collected in a clean beaker, butquickly the polymer-water mixture plugged the homogenization unit. Thehomogenizer module was reversed to clean the lines and returned back tothe normal position, but the mixture plugged again. The unit is designedto allow particles less than 200 μm pass.

The small stream of homogenized product was combined with the emulsifiedproduct and analyzed. The total amount of the acrylated polybutyleneproduced was 780 g ( expected to be about 1100 g). The loss of theproduct was due to the heat-up in the homogenization process.

EXAMPLE 8 Emulsification of Grounded Polyfunctional Polybutylene LR20878-129

The same 14 speed Osterizer blender was used to emulsify the groundpolyfunctional polybutylene. The blending was divided into two batches,with the same amount of the emulsified polymer produced (smaller volumein the blender made blending easier and more efficient).

294.0 g of distilled ionized water (49.0% of the total reactants) wascharged into a 1.0 liter beaker, 36.0 g of the surfactant No.23W004(6.0% of the total reactants) was added slowly into the beaker whilestirring. The surfactant-water mixture was poured into the blender.

270 g of polyfunctional polybutylene, id . no. LR20878-(yellow powder,45% of the total reactants) was charged into the blender by portions.The same procedure was followed to emulsify the mixture asemulsification of ground acrylated polybutylene. It took 40 minutes toemulsify all the acrylated polybutylene into yellow milky water mixture,the highest temperature reached inside the blender while blending themixture was 56° C.

The product particle size was mostly in the range of 10-30 μm with verysmall number of oversized particles. Some particles were reduced to 5 μmin size. This showed the polyfunctional polybutylene was emulsified muchbetter than the non-functional acrylated polybutylene. The particle sizewas analyzed using the same optical microscope.

The same batch was repeated the second time and the same product wasachieved. The total amount of the polyfunctional polybutylene producedwas 1120 g.

EXAMPLE 9

A modified polyethylene is made in accordance with the practice of thepresent invention by initially preheating 42 parts of low densitypolyethylene to a temperature of 110° C. The polyethylene was agitatedfor a period of about 5 minutes and a mixture of 1 part of the adduct ofmaleic anhydride and iminodiacetic acid and 0.042 part of dicumylperoxide was added to the polyethylene while it was stirred. After themixture was agitated for two minutes, the temperature of the mixture wasraised to 165° C. The resulting melt was then agitated for an additional10 minutes and then the molten polyethylene was removed. Based on methodof preparation, there was obtained maleic anhydride-iminodiacetic acidmodified polyethylene. The identity of the product is confirmed by itsinfrared spectrum and oxygen analysis.

EXAMPLE 10 Grafting of Polybutylene with Iminodiacetic Acid

Using a Brabender processor, 12 g of iminodiacetic acid and 48 g ofpolybutylene (PB8910 PC) are reacted as follows: Add 48 g of PBcontaining 2500 ppm of Lupersol 101 to mixing head and heat to about125° C. Then add slowly 12 g of iminodiacetic acid and allow to mix for15 minutes. The temperature of the mixture is then raised to 220° C. for15 minutes while stirring is maintained at 60 rpm. The product isremoved from the mixing head and allowed to cool.

NMR analysis of the resulting grafted material exhibits an extraaliphatic chemical shift peak at about 32 ppm (not seen in physicalmixture). The new peak is attributable to quaternary carbon formed bythe grafting of the IDA with the concomitant proton loss from the CHcarbon of the polybutylene.

It will be apparent from the foregoing that many other variations andmodifications may be made regarding the new polymers described herein,without departing substantially from the essential features and conceptsof the present invention. Accordingly, it should be clearly understoodthat the forms of the inventions described herein are exemplary only andare not intended as limitations on the scope of the present invention asdefined in the appended claims.

EXAMPLE 11 Preparation of Dimer ID. No.: LR24319-193

Into a three necked 500 ml flask there is added 25 grams of maleicanhydride pre-mixed with 67.9 g of iminodiacetic acid. The center jointcontained reflux tube with chilled water. The other two 24/40 joints onehad thermoweld to fit a k-type thermocouple the other was fitted with astopcock. The temperature was slowly raised at 0.66° C./min. to 180° C.using an Eurotherm 808 Controller. The temperature was held constant forone hour and then raised to 230° C. at 0.66 C/min. and held there for 1hr. A slight vacuum was pressed on the mixture for about 3-4 min.Product was poured into Teflon® coated tray and allowed to cool. Samplewas sent to the NMR lab for analysis. See scheme III.

EXAMPLE 12 Preparation of Trimer LR 24319-194

The reaction setup was similar to one discussed in EXAMPLE 11. Pre-mixed25 grams of maleic anhydride and 67.9 grams of iminodiacetic acid. Tothe mixture prior to heating we added 2500 ppm of Lupersol 101. Themixture was mixed well before heating. The heating was done in twosteps, the temperature was raised at 0.66° C./min to 140 C. held therefor 1 hour and then the temperature was raised to 180° C. at a rate of0.66° C./min. After holding the temperature for one hour a vacuum wasapplied to the mixture for 4-5 min. Vacuum was broken with nitrogen asproduct was poured into Teflon® coated tray and allowed to cool.

EXAMPLE 13 Preparation of Monomer LR. NO. 24319-194K

Same glassware arrangement was used in this set up as in Examples 11,12

Neutralization of the Aminodiacetic Acid

Neutralization of the aminodiacetic acid was done prior to the reactionwith the maleic anhydride.

Procedure

Into a 1000 ml beacker weigh 67.9 grams of the IDA. Add approximately300 grams of methanol and stir. Add slowly 147 ml of 3 N KOH. Allowmixture to react while stirring for 30 min. at room temperature. Filterthe product using a Whatmann paper no. 1. After filtration wash productwith three aliquots of chilled diethyl ether. Place product in oven setat 80 C. for one hour.

Preparation of the Monomer

Into a three necked 500 ml flask there is added 26.6 grams of maleicanhydride pre-mixed with 56.4 g of potassium iminodiacetic acid. Thecenter joint contained reflux tube with chilled water. The other two24/40 joints one had thermoweld to fit a k-type thermocouple the otherwas fitted with a stopcock. The temperature was slowly raised at 0.66C./min. to 180° C. using an Eurotherm 808 Controller. The temperaturewas held constant for one hour and then raised to 230° C. at 0.66 C/min.and held there for 1 hr. A slight vacuum was applied to the mixture forabout 34 min. Product was poured into a Teflon® coated tray and allowedto cool.

What is claimed is:
 1. A grafted polyolefin homopolymer or copolymercomprising the reaction product of: (a) a polyolefin homopolymer orcopolymer which had been grafted with an ethylenically unsaturatedmonomer having a functional group capable of reacting with an aminofunction; and (b) an amino carboxylic acid, with the proviso that saidethylenically unsaturated monomer of reactant (a) cannot be a glycidylsubstituted monomer.
 2. The grafted polyolefin product of claim 1,wherein said polyolefin is a maleic anhydride grafted polypropylene. 3.The grafted polyolefin product of claim 1, wherein said polyolefin is amaleic anhydride grafted polybutylene.
 4. The grafted polyolefin productof claim 1, wherein said polyolefin is a maleic anhydride graftedpolybutylene copolymer.
 5. The grafted polyolefin product of claim 4,wherein said polybutylene copolymer is a copolymer of 1-butene andethylene.
 6. The grafted polyolefin product of claim 5, wherein saidcopolymer contains 1-50 mole % ethylene.
 7. The grafted polyolefinproduct of claim 6, wherein said copolymer contains 1-30 mole %ethylene.
 8. The grafted polyolefin product of claim 2, wherein saidamino carboxylic acid is iminodiacetic acid.
 9. The grafted polyolefinproduct of claim 3, wherein said amino carboxylic acid is iminodiaceticacid.
 10. The grafted polyolefin product of claim 7, wherein said aminocarboxylic acid is iminodiacetic acid.
 11. A grafted polyolefincomprising the reaction product of: (a) a polyolefin; (b) anethylenically unsaturated monomer having a functional group capable ofreacting with an amino function, with the proviso that saidethylenically unsaturated monomer (b) cannot be a glycidyl substitutedmonomer; and (c) an amino carboxylic acid.
 12. The grafted polyolefinproduct of claim 11, wherein said polyolefin is polybutene, saidethylenically unsaturated monomer is maleic anhydride and said aminocarboxylic acid is iminodiacetic acid.
 13. The grafted polyolefinproduct of claim 11, wherein said polyolefin is a copolymer of 1-butenecontaining 1-30 mole % ethylene, said ethylenically unsaturated monomeris maleic anhydride and said amino carboxylic acid is iminodiaceticacid.
 14. A composition comprising: (a) a polyolefin polymer orpolyolefin copolymer; (b) a grafting compound selected from the groupconsisting of vinyl polymerizable, unsaturated, hydrolyzable silanes;carboxylic acids; carboxylic acid derivatives; carboxylic acidanhydrides; carboxylic acid anhydride derivatives; and mixtures thereof,with the proviso that said grafting compound cannot be a glycidylsubstituted vinyl polymerizable compound; (c) an amino carboxylic acid;and (d) a free radical generator.
 15. The composition of claim 14wherein said polyolefin (a) is a copolymer of 1-butene and 1-30 mole %ethylene; said grafting compound (b) is maleic anhydride; said aminocarboxylic acid (c) is iminodiacetic acid; and (d) said free radicalgenerator is 2,5-dimethyl-2,5-di-(tert-butylperoxy)-hex-3-yne.